Model Compounds for Intermediates and Transition States in Sonogashira and Negishi Coupling: d⁸–d¹⁰ Bonds in Large Heterobimetallic Complexes Are Weaker than Computational Chemistry Predicts

We report an experimental study, with accompanying DFT calculations, on a series of heterobimetallic complexes with Pd­(II) and Cu­(I), Ag­(I), or Au­(I). The isolable pincer complexes are models for the intermediates and transition state for the transmetalation step in Sonogashira and Negishi coupling reactions, among which, according to the DFT calculations, only the transition state has the two metal centers within bonding distance. Furthermore, we report a substituted version of an analogous heterobimetallic complex in which a competing dissociation sets an upper-bound on the strength of the d⁸–d¹⁰ metal–metal bond. Analysis of the structures in the solid state and in solution, and the competitive dissociation experiment in the gas phase, indicate that the dispersion-corrected DFT method used in the study appears to overestimate the strength of the metal–metal interaction, thus distorting the shape of the computed potential energy surface systematically for transmetalation.